Long lasting cosmetic compositions

ABSTRACT

Provided herein are long lasting hair compositions, color enhancers, and markers for selecting the same.

RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application No.62/655,273, filed Apr. 10, 2018 and U.S. Provisional Application No.62/557,823, filed Sep. 13, 2017, the entire contents of each of whichare incorporated herein by reference.

BACKGROUND

Polyurethanes are a well-known class of synthetic polymers with broadutility in multiple industries. This versatility is derived from theability to prepare polyurethanes from a large and diverse set ofpotential monomers. These diverse monomer options allow the realizationof an equally diverse set of physical properties. Hence, the resultingpolyurethanes can be in many different forms including e.g., soft foams,elastomers, adhesive films, or hard plastics, and can be used in manydifferent types of products including bedding, foot wear, adhesives, andautomobile parts. Among these many forms of polyurethanes, waterbornepolyurethanes (WBPUs) have been used as film forming agents incommercially available personal care products.

A problem with the use of WBPUs has been the lack of performance andoverall consistency in application. For example, common polyurethaneproducts such as Luviset® P.U.R (Polyurethane-1), DynamX, and DynamX/H₂O(Polyurethane-14 and AMP-Acrylates Copolymer) lack elasticity. Thisleads to an undesirable stiff feeling when applied to hair. Avalure UR450 (PPG-17/IPDI/DMPA Copolymer), Baycusan C1004 (Polyurethane-35),Baycusan C1008 (Polyurethane-48), and Polyderm PE/PA ED(Polyurethane-58), on the other hand, are very flexible (i.e., do notlack elasticity). These products, however, have poor initial curl holdand elicit a gummy feeling. Other problems associated with the use ofWBPUs include e.g., flaking upon touching or combing (e.g., dustymicro-flakes shown on hair fibers); undesirable tactile feelings upontouch (e.g., brittle, stiff, or tacky, gummy); poor humidity resistance(e.g., styling resins absorb moisture and weigh down hair resulting in aloss of style); lack of movement (e.g., plastic-like mold shape; haircurls don't move with motion; can't easily comb through; gummy; lack ofbounciness); and short-lived hair styles (e.g., hair styles, curls,waves, etc. don't last long—on average styles typically last less than ahalf day).

There is therefore a need for improved and more consistent WBPU-basedpersonal care products including e.g., ones that provide enhanced hold,high humidity curl retention, and/or positive sensory attributes.

SUMMARY

A specific combination of selection markers for cationic polyurethaneshave now been identified that result in cosmetic compositions (e.g.,hair products) which have substantially improved performance and whichcan be used in a variety of applications. Markers for these cationicpolymers include e.g., a Young's modulus above 150 MPa, an elongation atbreak from about 15% to about 300%, and a moisture uptake of less than10%.

In one aspect, the disclosed cationic polyurethanes can be used in atwo-wave hair styling process comprising anionic polyurethanes. Applyingand fixing the disclosed cationic polyurethanes to the hair prior to theapplication of anionic polyurethanes was found to enhance hold, highhumidity curl retention, and positive sensory attributes. See e.g., FIG.2 to FIG. 6.

In another aspect, the disclosed cationic polyurethanes can serve asadditives for conditioners or leave-in-conditioners. When used in thismanner, the disclosed cationic polyurethanes were found to providebetter hold, improve stylability, minimize flyaways, and to sustainnatural curl enhancement. See e.g., FIG. 7 to FIG. 10.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an illustration of a two-wave styling process using thecationic polyurethanes described herein.

FIG. 2a shows an example of hair tresses before and after high humiditytest styled using two-wave cationic/anionic application describedherein. FIG. 2b shows the lengths of curls measured before and afterhigh humidity testing for tresses treated either with two-wave stylingwith cationic and anionic WBPUs vs. one-wave application of eithercationic or anionic WBPUs. The best initial hold and the best curlretention after high humidity was observed in set B (two-wave styling;cationic WBPU followed by anionic WBPU; (+)/(−)) as opposed to thetresses styled using (+) or (−) WBPUs alone or in the opposite order((−)/(+)).

FIG. 3 shows the results of mannequin testing using aqueous dispersionsof cationic polyurethanes using the two-wave method described herein.The two-wave styling (+/−) was applied on the left side using arepresentative cationic WBPU PU 377 as the first wave and anionic WBPUas the second wave, showing better curl hold, curl shape, and curldefinition compared to the application on the right side of anionic WBPUin both waves (−/−). A blinded, trained sensory evaluator determinedthat the curls generated using the (+/−) two-wave treatment wasaesthetically preferable to the curls generated using the (−/−)treatment.

FIG. 4 shows the results of mannequin testing using cationicpolyurethanes in different styling formulations using the two-wavemethod described herein. The two-wave styling (+/−) applied on the rightside of the mannequin head showed better initial curl hold, curl shape,and better curl retention after humidity testing than the application onthe left where a control formulation as the first wave and anionic WBPUas the second wave (Ctrl/−) was used. The curls made with the (Ctrl/−)treatment fell significantly compared to the two-wave (+/−) treatment. Ablinded, trained sensory evaluator determined that the style obtainedusing the (+/−) two-wave treatment was aesthetically preferable to thestyle obtained using the (Ctrl/−) treatment.

FIG. 5 shows in vivo testing showing better initial hold and highhumidity curl retention using aqueous dispersions of cationicpolyurethanes by two-wave styling described herein. Curls on the leftside of the panelist head showed better curl retention after humiditytest with (+/−) two-wave styling application, while curls on the rightside of the panelist head lost their shape and fell more loosely wherethe (−/−) application was performed. A blinded, trained sensoryevaluator determined that the curls generated using the (+/−) two-wavetreatment were aesthetically preferable to the curls generated using the(−/−) treatment.

FIG. 6 shows in vivo testing showing better natural curl definitionusing cationic polyurethanes in different styling formulations bytwo-wave styling described herein. Natural curls of the panelist areenhanced and appear less frizzy on the left side where (+/−) two-wavestyling was applied, while curls on the right side of the panelistappear less defined and less desirable where a control formulation onlywas applied. A blinded, trained sensory evaluator determined that thestyle obtained with the (+/−) two-wave treatment was aestheticallypreferable to the style obtained with the control treatment.

FIG. 7 shows an example of the curls generated using a hot curling iron,on hair washed with conditioner containing 5% cationic polyurethane(left) or with the same conditioner without a cationic polyurethane. Thecurl hold is significantly better on the left side of the panelist wherethe formulation with cationic polyurethane was applied—the curls havebetter definition, shape and bounce. Curls are limper and looser on theright side where conditioner base alone was applied. A blinded, trainedsensory evaluator determined that the curls generated using conditionercontaining cationic WBPU was aesthetically preferable to the curlsgenerated using the conditioner alone.

FIG. 8 illustrates the blowout stylability performance of hair washedwith conditioner comprising 5% cationic polyurethane as describedherein. The style on the left, which was done on hair treated with theconditioner containing cationic WBPU, shows better body and shape afterstyling with a round brush—the hair curls naturally where the brush wasused, which is a desirable effect of a blowout style. The blowout styledone on the hair treated with conditioner alone (right) has less styledefinition, more frizziness, and less volume. A blinded, trained sensoryevaluator determined that the style obtained using conditionercontaining cationic WBPU was aesthetically preferable to the styleobtained using the conditioner alone.

FIG. 9 shows minimization of flyaways on hair treated with conditionercomprising 5% cationic polyurethane as described herein applied on theright side of the panelist. The hair treated with the conditionercomprising cationic polyurethane (right) lies smoother after drying andhas improved shine and manageability. A blinded, trained sensoryevaluator determined that this style obtained using conditionercontaining cationic WBPU was aesthetically preferable to the styleobtained using the conditioner alone.

FIG. 10 shows natural curl retention on hair treated with conditionercomprising 5% cationic polyurethane as described herein. The hairtreated with the conditioner comprising cationic polyurethane (right)shows better natural curls enhancement and manageability compared to thehair treated with the conditioner alone, which was frizzier and had poorcurl shape. A blinded, trained sensory evaluator determined that thisstyle obtained using conditioner containing cationic WBPU wasaesthetically preferable to the style obtained using the conditioneralone.

DETAILED DESCRIPTION 1. Definitions

A composition, process, or method described herein that “consistsessentially of” a cationic polyurethane and other components means thatthe recited cationic polyurethane is the only polyurethane present inthe recited composition, process, or method. Thus, “consists essentiallyof” or “consisting essentially of” is open ended for all terms exceptfor the inclusion of additional polyurethanes, i.e., only the recitedcationic polyurethane is present.

A composition, process, or method described herein that “consists of” acationic polyurethane and other components means that only the recitedcomponents are present. In other words, “consisting of” excludes anyelement, step, or ingredient not specified. “Consists of” and“consisting of” are used interchangeably.

“Comprising” is inclusive or open-ended and does not exclude additional,un-recited elements or method steps.

As used herein, “cationic polyurethanes” refer to thermoplastic polymerscomprising carbamate (urethane) groups and which bear an overall netpositive charge at pH<7. In some aspects, the cationic polyurethanesdescribed herein bear an overall net positive charge at pH from about3.7 to about 6.5, from about 3.7 to about 6.0, or from about 3.7 toabout 5.5. Unless otherwise specified, cationic polyurethanes, when usedherein, include amphoteric/cationic polyurethanes. In one aspect,however, cationic polyurethanes do not encompass amphoteric/cationicpolyurethanes.

As used herein, “anionic polyurethanes” refer to thermoplastic polymerscomprising carbamate (urethane) groups and which bear an overall netnegative charge at pH>7. Unless otherwise specified, anionicpolyurethanes, when used herein, include amphoteric/anionicpolyurethanes. In one aspect, however, anionic polyurethanes do notencompass amphoteric/anionic polyurethanes.

As used herein, “amphoteric polyurethanes” refer to thermoplasticpolymers comprising carbamate (urethane) groups and which can act as acationic or anionic polyurethane. An “amphoteric/cationic polyurethane”means that the described amphoteric species is one which is acting as anacid under the defined methods and/or conditions. Similarly, an“amphoteric/anionic polyurethane” means that the described amphotericspecies is one which is acting as a base under the defined methodsand/or conditions.

“Young's modulus (or the modulus of elasticity, tensile modulus)” is ameasure of the stiffness of a solid polymer film. Young's modulus, E,can be calculated by dividing the tensile stress by the extensionalstrain in the elastic (initial, linear) portion of the stress-straincurve. The Young's modulus of the cationic polyurethane can bedetermined by a protocol defined to measure mechanical properties, andis developed in reference to ASTM D638, ASTM D412, test guidelines asdescribed below in Example 2.

The “elongation at break (also known as fracture strain, ultimateelongation)” is the ratio between changed length and initial lengthafter breakage of the solid polymer film. The elongation at break of thecationic polyurethane can be determined by a protocol defined to measuremechanical properties, and is developed in reference to ASTM D638, ASTMD412, test guidelines as described below in Example 2.

The “moisture uptake” is the measure of water adsorbed by the solidpolymer film. The method for determining the moisture uptake of thesolid polymer film is provided in Example 3.

The “sensory score” is determined by the performance of the hairfixative. In particular, the tress with the composition applied is blowdried for 90 seconds. The tresses are prepared in duplicate and blindedrandomly and evaluated for natural feeling and overall sensoryattributes on a scale of −2 to 2 by trained sensory analysts underblinded conditions. Sensory analysts are licensed hair stylists andcosmetic scientists with significant long-term experience evaluatingsensory attributes of hair. Sensory analysts assign a score of −2 totresses deemed entirely undesirable, a score of +2 to entirely soft,natural feeling and appearing hair, and intermediate scores betweenthese two extremes.

2. Selection Markers

Provided herein are specific combinations of WBPU properties that havebeen found to result in cosmetic compositions (e.g., hair products)having substantially improved performance. Those properties includee.g., a combination of certain mechanical properties, a combination ofcertain chemical properties, or a combination of both mechanical andchemical properties.

Young's Modulus, Elongation at Break, and Moisture Uptake

The combination of mechanical properties described herein include theYoung's modulus (e.g., above 150 MPa), the elongation at break (e.g.,from about 15% to about 300%), and hydrophobicity (moisture uptake,e.g., less than 10%).

In one aspect, the Young's modulus of the cationic polyurethane shouldbe above about 150 MPa. For example, the Young's modulus of the cationicpolyurethane in the disclosed compositions may be above about 160 MPa,above about 170 MPa, above about 180 MPa, above about 190 MPa, aboveabout 200 MPa, above about 210 MPa, above about 220 MPa, above about 230MPa, above about 240 MPa, above about 250 MPa, above about 260 MPa,above about 270 MPa, above about 280 MPa, above about 290 MPa, aboveabout 300 MPa, above about 310 MPa, above about 320 MPa, above about 330MPa, above about 340 MPa, above about 350 MPa, above about 360 MPa,above about 370 MPa, above about 380 MPa, above about 390 MPa, aboveabout 400 MPa, above about 410 MPa, above about 420 MPa, above about 430MPa, above about 440 MPa, above about 450 MPa, above about 460 MPa,above about 470 MPa, above about 480 MPa, above about 490 MPa, aboveabout 500 MPa, above about 510 MPa, above about 520 MPa, above about 530MPa, above about 540 MPa, or above 550 MPa. In other aspects, theYoung's modulus of the cationic polyurethane should be between about 150MPa and about 500 MPa. For example, the Young's modulus of the cationicpolyurethane in the disclosed compositions may be between about 150 MPaand about 400 MPa, between about 150 MPa and about 350 MPa, betweenabout 170 MPa and about 390 MPa, between about 180 MPa and about 320MPa, between about 190 MPa and about 300 MPa, between about 200 MPa andabout 290 MPa, or between about 210 MPa and about 280 MPa.

In one aspect, the elongation at break of the cationic polyurethaneshould be from about 15% to about 300%. For example, the elongation atbreak of the cationic polyurethane in the disclosed composition may befrom about 20% to about 300%, from about 25% to about 300%, from about40% to about 280%, from about 100% to about 280%, from about 100% toabout 250%, from about 150% to about 250%, from about 200% to about250%, from about 210% to about 250%, about 30% to about 150%, from about15% to about 150%, from about 150% to about 300%, from about 50% toabout 250%; from about 75% to about 225%, or from about 100 to about200%. The elongation break may be optionally combined with one or moreof the Young's modulus values described in the paragraph above or anyone of the Young's modulus values described in the remainder of thedisclosure.

In one aspect, the moisture uptake of the cationic polyurethane shouldbe less than about 10%. For example, the moisture uptake of the cationicpolyurethane in the disclosed compositions may be less than about 9.5%,less than about 9%, less than about 8.5%, less than about 8%, less thanabout 7.5%, less than about 7%, less than about 6.5%, less than about6%, less than about 5.5%, less than about 5%, less than about 4.5%, lessthan about 4%, less than about 3.5%, less than about 3%, less than about2.5%, less than about 2%, less than about 1.5%, less than about 1%, lessthan about 0.5%, or is about 0%. In one aspect, the moisture uptake ofthe cationic polyurethane in the disclosed compositions should be fromabout 0% to about 10%. For example, the moisture uptake may be fromabout 0% to about 8%, from about 2% to about 8%, or from about 3% toabout 7%. The moisture uptake may be optionally combined with one ormore of the Young's modulus values, one or more of the elongation breakvalues, or both as described in the paragraphs above or in the remainderof the disclosure.

As shown in the Exemplification section below, cationic polyurethaneshaving the Young's modulus, elongation at break, and moisture uptakedescribed above have improved performance (e.g., enhanced hold, highhumidity curl retention, positive sensory attributes, improvedstylability, natural curl enhancement, and minimization of flyaways.

Additional Indicators

In addition to the Young's modulus, elongation at break, and moistureuptake, other indicators may be used to identify the capability ofcationic polyurethanes to provide long lasting, moisture-resistant holdhair product with favorable sensory attributes. Such indicators includee.g., change in tress length and sensory score.

Thus, in certain aspects, the cationic polyurethane may be selected suchthat the composition, after being applied to a curled hair tress anddried thereon, provides less than about 80% change in tress length asmeasured by the high humidity mechanical stress test. For example, thecationic polyurethane may be selected such that the composition, afterbeing applied to a curled hair tress and dried thereon, provides lessthan about 75%, about 70%, about 65%, about 60%, about 55%, about 50%,about 45%, about 40%, about 35%, about 30%, about 25%, about 20%, about15%, about 10%, about 5%, or about 0% change in tress length as measuredby the high humidity mechanical stress test. The change in tress lengthas described herein may also be combined with any one of the Young'smodulus values, elongation at break values, and moisture uptake valuesdescribed above and herein.

In other aspects, the cationic polyurethane may be selected such thatthe composition, after being applied to a hair tress and dried thereon,provides a sensory score of at least about 0. For example, the cationicpolyurethanes in the disclosed compositions may be selected such thatthe composition, after being applied to a hair tress and dried thereon,provides a sensory score of at least about 0.1, about 0.2, about 0.3,about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about1.0, about 1.1, about 1.2, about 1.3, about 1.4, or about 1.5. Thesensory score feature as described herein may also be combined with anyone of the change in tress length values, the Young's modulus values,the elongation at break values, and the moisture uptake values describedabove and herein.

As shown in the Exemplification section below, cationic polyurethaneshaving the Young's modulus, elongation at break, and moisture uptakedescribed above, and optionally one or more of the alternativeindicators (e.g., sensory score, change in tress length, etc.) providehair styling products with improved mechanical properties, sensoryproperties and performance.

3. Compositions

Provided herein are compositions (e.g., hair treatment compositions)comprising a cationic polyurethane having a Young's modulus above 150MPa, an elongation at break from about 15% to about 300%, and a moistureuptake of less than 10%. Also provided are composition consistingessentially of a cationic polyurethane; a neutralizer; and an oil,wherein the cationic polyurethane has a Young's modulus above 150 MPa;an elongation at break from about 15% to about 300%; and a moistureuptake of less than 10%.

In some aspects, the cationic polyurethane in the provided compositionsis a salt of the formula: [W, V, Y and Z]X⁻, wherein W is the productformed from polycarbonate polyol monomer; V is the product formed frompolyisocyanate monomer; Y is the product formed from C₁₋₈alkyldiolmonomer; Z is the product formed from C₁₋₈aminoalkyldiol monomer; X is aneutralizing ion; the molecular weight of W is about 1,000 g/mol; themolar ratio of V:W is 1:0.18 to about 1:0.32; the molar ratio of V:Y is1:0.24 to about 1:0.72; and the molar ratio of V:Z is 1:0.08 to about1:0.47. In one alternative, the cationic polyurethane in the providedcompositions is a salt of the formula: [W, V, Y and Z]X⁻, wherein W isthe product formed from polycarbonate polyol monomer; V is the productformed from polyisocyanate monomer; Y is the product formed fromC₁₋₈alkyldiol monomer; Z is the product formed from C₁₋₈aminoalkyldiolmonomer; X is a neutralizing ion; the molecular weight of W is about2,000 g/mol; the molar ratio of V:W is 1:0.08 to about 1:0.18; the molarratio of V:Y is 1:0.36 to about 1:0.82; and the molar ratio of V:Z is1:0.08 to about 1:0.49. In another alternative, the cationicpolyurethane in the provided compositions is a salt of the formula: [W,V, Y and Z]X⁻, wherein W is the product formed from polycarbonate polyolmonomer; V is the product formed from polyisocyanate monomer; Y is theproduct formed from C₁₋₈alkyldiol monomer; Z is the product formed fromC₁₋₈aminoalkyldiol monomer; X is a neutralizing ion; the molecularweight of W is about 3,000 g/mol; the molar ratio of V:W is 1:0.05 toabout 1:0.13; the molar ratio of V:Y is 1:0.4 to about 1:0.85; and themolar ratio of V:Z is 1:0.08 to about 1:0.49.

In one alternative the cationic polyurethane is a salt of the formula:[W, V, Y, Z, and Z¹]X⁻, wherein W is the product formed frompolycarbonate polyol monomer; V is the product formed frompolyisocyanate monomer; Y is the product formed from C₁₋₈alkyldiolmonomer; Z is the product formed from C₁₋₈aminoalkyldiol monomer; Z¹ isthe product formed from ethoxylated polyol monomer; X is a neutralizingion; the molecular weight of W is about 1,000 g/mol; the molar ratio ofV:W is 1:0.19 to about 1:0.33; the molar ratio of V:Y is 1:0.19 to about1:0.7; the molar ratio of V:Z is 1:0.08 to about 1:0.49; and the molarratio of V:Z¹ is 1:0 to about 1:0.03. In another alternative, thecationic polyurethane in the provided compositions is a salt of theformula: [W, V, Y, Z, and Z¹]X⁻, wherein W is the product formed frompolycarbonate polyol monomer; V is the product formed frompolyisocyanate monomer; Y is the product formed from C₁₋₈alkyldiolmonomer; Z is the product formed from C₁₋₈aminoalkyldiol monomer; Z¹ isthe product formed from ethoxylated polyol monomer; X is a neutralizingion; the molecular weight of W is about 2,000 g/mol; the molar ratio ofV:W is 1:0.09 to about 1:0.18; the molar ratio of V:Y is 1:0.31 to about1:0.8; the molar ratio of V:Z is 1:0.09 to about 1:0.51; and the molarratio of V:Z¹ is 1:0 to about 1:0.03. In another alternative, thecationic polyurethane in the provided compositions is a salt of theformula: [W, V, Y, Z, and Z¹]X⁻, wherein W is the product formed frompolycarbonate polyol monomer; V is the product formed frompolyisocyanate monomer; Y is the product formed from C₁₋₈alkyldiolmonomer; Z is the product formed from C₁₋₈aminoalkyldiol monomer; Z¹ isthe product formed from ethoxylated polyol monomer; X is a neutralizingion; the molecular weight of W is about 3,000 g/mol; the molar ratio ofV:W is 1:0.05 to about 1:0.13; the molar ratio of V:Y is 1:0.36 to about1:0.83; the molar ratio of V:Z is 1:0.09 to about 1:0.52; and the molarratio of V:Z¹ is 1:0 to about 1:0.03. In another alternative, thecationic polyurethane in the provided compositions is a salt of theformula: [W, V, Y, Z, and Z²]X⁻, wherein W is the product formed frompolycarbonate polyol monomer; V is the product formed frompolyisocyanate monomer; Y is the product formed from C₁₋₈alkyldiolmonomer; Z is the product formed from C₁₋₈aminoalkyldiol monomer; Z² isthe product formed from hydroxylated alkyl acid monomer; X is aneutralizing ion; the molecular weight of W is about 1,000 g/mol themolar ratio of V:W is 1:0.19 to about 1:0.33; the molar ratio of V:Y is1:0.14 to about 1:0.44; the molar ratio of V:Z is 1:0.08 to about1:0.47; and the molar ratio of V:Z² is 1:0.05 to about 1:0.33. Inanother alternative, the cationic polyurethane in the providedcompositions is a salt of the formula: [W, V, Y, Z, and Z²]X⁻, wherein Wis the product formed from polycarbonate polyol monomer; V is theproduct formed from polyisocyanate monomer; Y is the product formed fromC₁₋₈alkyldiol monomer; Z is the product formed from C₁₋₈aminoalkyldiolmonomer; Z² is the product formed from hydroxylated alkyl acid monomer;X is a neutralizing ion; the molecular weight of W is about 2,000 g/mol;the molar ratio of V:W is 1:0.09 to about 1:0.18; the molar ratio of V:Yis 1:0.26 to about 1:0.53; the molar ratio of V:Z is 1:0.09 to about1:0.49; and the molar ratio of V:Z² is 1:0.05 to about 1:0.35. Inanother alternative, the cationic polyurethane in the providedcompositions is a salt of the formula: [W, V, Y, Z, and Z²]X⁻, wherein Wis the product formed from polycarbonate polyol monomer; V is theproduct formed from polyisocyanate monomer; Y is the product formed fromC₁₋₈alkyldiol monomer; Z is the product formed from C₁₋₈aminoalkyldiolmonomer; Z² is the product formed from hydroxylated alkyl acid monomer;X is a neutralizing ion; and the molecular weight of W is about 3,000g/mol; the molar ratio of V:W is 1:0.05 to about 1:0.13; the molar ratioof V:Y is 1:0.3 to about 1:0.56; the molar ratio of V:Z is 1:0.09 toabout 1:0.5; and the molar ratio of V:Z² is 1:0.05 to about 1:0.35.

In yet another alternative, V is the product formed from isophoronediisocyanate monomer; Y is the product formed from 1,4-butanediolmonomer; and Z is the product formed from3-(dimethylamino)-1,2-propanediol monomer. In yet another alternative,the cationic polyurethane is a salt of the formula:

wherein n is 6 to 21 and m is 19 to 31.

In some aspects, the cationic polyurethane in the provided compositionsis selected from PU-363, PU-399, PU-400, PU-377, PU-404, PU-378, PU-383,PU-398, PU-401, PU-402, PU-403, PU-385, PU-376, PU-408, PU-409, PU-396,PU-413, PU-414, PU-362, and PU-372. In another aspect, the cationicpolyurethane is selected from PU-362, PU-376, PU-377, PU-378, andPU-404. In yet another aspect, the cationic polyurethane is selectedfrom PU-363, PU-377, and PU-378.

Also provided is a hair treatment composition comprising a cationicpolyurethane having the formula:

wherein n is 6 to 21 and m is 19 to 31.

Further provided is a hair treatment composition consisting essentiallyof a cationic polyurethane having the formula:

wherein n is 6 to 21 and m is 19 to 31; a neutralizer; and an oil.

In some aspects, the cationic polyurethane is dispersed in water.

In some aspects, the cationic polyurethane is in the form of a particle.

In some aspects, the cationic polyurethane comprises uniform particleshaving an average particle diameter of about 20 to about 80 nm.

In some aspects, the cationic polyurethane comprises bimodal ormultimodal particles having an average particle diameter of about 100 toabout 300 nm.

In some aspects, the cationic polyurethane is present in an amount of25% to 35% based on the total weight of the composition.

In some aspects, the compositions described herein further comprise aneutralizer. The neutralizer may be e.g., an acid neutralizer such aslactic acid. In some aspects, the neutralizer:C₁₋₈aminoalkyldiol monomerratio is from about 0.8 to about 1.2.

In some aspects, the compositions described herein further comprise anoil. Oils for use in the disclosed compositions can be selected frommineral, animal, plant or synthetic oils. In one aspect, the oil islinoleic acid or a mixture of fatty acids. Examples include, but are notlimited to fragrance oils, emollients, monoterpenoids, fatty alcohols,fatty acids, fatty esters, fatty ethers, fluorinated small molecules(e.g., perfluoromethylcyclopentane, perfluoroperhydrophenanthrene,perfluoro-1,3-dimethylcyclohexane, perfluoromethyldecalin, andperfluoroperhydrobenzyltetralin), and mixtures thereof. In anotheraspect, the oil is present in an amount ranging from about 0.2 to about1.65% based on the total weight of the composition. In another aspect,the oil is present in an amount of about 0.2 to about 0.25% based on thetotal weight of the composition.

In one aspect, the disclosed compositions are applied to the hair withwater.

In one aspect, the disclosed compositions, when applied to the hair,change the texture and appearance.

In one aspect, the disclosed compositions, when applied to the hair,improve hold, i.e., hair that is formed into a given curl or styleretains that curl or style over time.

In one aspect, the disclosed compositions, when applied to the hair,provide sufficient stylability, i.e., the composition applied to hairsupplies sufficient rigidity and flexibility to form and maintain astyle.

In one aspect, the disclosed compositions, when applied to the hair,minimize flyaways, i.e., there are minimal individual hair fibers thatdo not conform to the given curl or style.

In one aspect, the disclosed compositions, when applied to the hair,preserves curl shape, i.e., hair that is formed into a given curlretains that curl over time.

In one aspect, the disclosed compositions, when applied to the hair,provides natural curl enhancement, i.e., hair that naturally tends tocurl displays a more defined and less diffused curl pattern.

The compositions described herein may further comprise an antioxidant.

Antioxidants that may be suitable with the compositions described hereininclude, but are not limited to, acai oil, alpha lipoic acid, green andwhite tea, retinol, vitamin C, Vitamin E, butylated hydroxytoluene,butylated hydroxyanisole, coenzyme Q10 (Co Q-10), isoflavones,polyphenols, curcumin, turmeric, pomegranate, rosemary, glutathione,selenium, and zinc.

4. Methods of Use

The compositions described herein may be used for any cosmeticapplication. Such applications include, but are not limited to,skin-care creams, eye and facial makeup (e.g., mascara, eye liner,eyebrow makeup, and the like), deodorants, lotions, powders, perfumes,baby products, body butters; and hair products (e.g., permanentchemicals, hair colors, hair sprays, and gels).

In one aspect, the compositions described herein are used as a hairproduct, e.g., in a conventional manner for providing hairstyle/holdbenefits.

In an exemplary aspect, an effective amount of a composition describedherein may be sprayed or applied onto dry or damp hair before and/orafter the hair is styled. As used herein “effective amount” means anamount sufficient to provide the hair hold and style performance desiredaccording to the length and texture of the hair.

In one aspect, the present disclosure provides a method of fixing haircomprising the step of applying a polyurethane disclosed herein. In oneaspect, the present disclosure provides a method of retaining the curlof hair comprising the step of applying polyurethane disclosed herein.

In one aspect, the present disclosure also includes a method todetermine the curl retention of a hair tress. In one aspect, the methodof measuring the curl retention of a hair tress includes the steps of a)measuring the length of the hair tress; b) applying a compositioncomprising a waterborne polyurethane disclosed herein to the hair tress;c) blow drying the hair tress for 90 seconds without brushing; d)curling the hair tress with a ¾ inch curling rod at 370° F. for 10seconds; e) mechanically manipulating the hair tress by pulling, combingand brushing; f) measuring the length of the curled hair tress.

In one aspect, the method of measuring the curl retention of a hairtress, includes the steps of a) measuring the length of the hair tress;b) applying the composition comprising a waterborne polyurethanedisclosed herein to the hair tress; c) blow drying the hair tress for 90seconds without brushing; d) curling the hair tress with a ¾ inchcurling rod at 370° F. for 10 seconds; e) subjecting the hair tress tohumidity; f) measuring the length of the curled hair tress. In oneaspect, the curled hair tress is subjected to 60%, 70%, 75%, 80% or 90%relative humidity for 3, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60,75, 90, 105, 120, 180 or 210 minutes at a temperature of 25° C.

In one aspect, the method of measuring the curl retention of a hairtress, includes the steps of a) measuring the length of the hair tress;b) applying the composition comprising a waterborne polyurethanedisclosed herein to the hair tress; c) blow drying the hair tress for 90seconds without brushing; d) curling the hair tress with a ¾ inchcurling rod at 370° F. for 10 seconds; e) subjecting the hair tress tohumidity; f) brushing the hair tress; g) measuring the length of thecurled hair tress. In a particular aspect, the curled hair tress issubjected to 60%, 70%, 75%, 80% or 90% relative humidity for 2, 4, 8,16, 32, or 48 hours at a temperature of 25° C. and brushed 1, 3, 5, 8,10, 13, 15, or 20 times.

In one aspect, the method of evaluating the curl retention of a hairtress, includes the steps of a) applying the composition comprising apolyurethane disclosed herein to the hair tress; b) blow drying the hairtress for 90 seconds without brushing; c) blinding the prepared hairtress; d) evaluating the sensory properties of the tress in a blindedfashion. In one aspect, the prepared tress is graded on a scale of −2 to2 for natural feeling and overall sensory attributes.

In one aspect, the cationic polymers described herein are for use in aconditioner or leave-in-conditioner.

In one aspect, provided is a method for styling hair comprising a)applying a cationic polyurethane-based composition described herein (theso-called “first wave”; b) heating the hair to a temperature sufficientto induce curl; and c) applying an anionic polyurethane having a Young'smodulus above 150 MPa, an elongation at break from about 15% to about300%, and a moisture uptake of less than 10% (the so-called “secondwave”). In one aspect, steps a), b), and c) are repeated.

EXEMPLIFICATION Example 1. Chemical Compositions of Cationic WaterbornePolyurethane

Cationic waterborne polyurethanes were synthesized primarily usingpolycarbonate diol, 1,4-butanediol (BD), isophorone diisocyanate (IPDI),and 3-(dimethylamino)-1,2-propanediol (DMAPD); selectively, the nonionicchain extenders Tegomer D3403 (ethoxylated polyether-1,3-diol) and2,2-bis(hydroxymethyl)butyric acid (DMBA) were incorporated in cationicwaterborne polyurethanes respectively to achieve desired physicalproperties. A mild acid, lactic acid, was used as a neutralizer. Foreach monomer, the molar ratio to NCO is listed in Table 1. Moreover, abeneficial oil could be also incorporated into cationic waterbornepolyurethanes to provide improved sensory attributes.

TABLE 1 Other diol Ionic chain Nonionic chain Polyol segment extenderextender PU (molar ratio (molar ratio (molar ratio (molar ratio DegreeName NCO to NCO) to NCO) to NCO) to NCO) Neut. of Neut. Oil 363 IPDIPCD1K_0.29 BD_0.27 DMAPD_0.45 N/A Lactic acid 100% N/A 399 IPDIPCD1K_0.29 BD_0.26 DMAPD_0.44 N/A Lactic acid 100% N/A 400 IPDIPCD1K_0.20 BD_0.42 DMAPD_0.38 N/A Lactic acid 100% N/A 377 IPDIPCD1K_0.28 BD_0.42 DMAPD_0.30 N/A Lactic acid 100% N/A 404 IPDIPCD1K_0.29 BD_0.41 DMAPD_0.30 N/A Lactic acid 100% N/A 378 IPDIPCD1K_0.28 BD_0.51 DMAPD_0.21 N/A Lactic acid 100% N/A 383 IPDIPCD1K_0.28 BD_0.61 DMAPD_0.12 N/A Lactic acid 100% N/A 398 IPDIPCD1K_0.29 BD_0.58 DMAPD_0.12 Tegomer_0.0049 Lactic acid 100% N/A 401IPDI PCD1K_0.29 BD_0.60 DMAPD_0.12 N/A Lactic acid 100% N/A 402 IPDIPCD3K_0.10 BD_0.78 DMAPD_0.12 N/A Lactic acid 100% N/A 403 IPDIPCD1K_0.30 BD_0.26 DMAPD_0.44 N/A Lactic acid  80% N/A 385 IPDIPCD1K_0.28 BD_0.61 DMAPD_0.12 N/A Lactic acid 110% N/A 376 IPDIPCD1K_0.29 BD_0.27 DMAPD_0.45 N/A Lactic acid 100% Linoleic acid 408IPDI PCD1K_0.28 BD_0.42 DMAPD_0.30 N/A Lactic acid 100% Linoleic acid409 IPDI PCD1K_0.28 BD_0.42 DMAPD_0.30 N/A Lactic acid 100% Mixture ofFAs 396 IPDI PCD1K_0.28 BD_0.61 DMAPD_0.12 N/A Lactic acid 100% Linoleicacid 413 IPDI PCD1K_0.20 BD_0.56 DMAPD_0.25 N/A Lactic acid 100% N/A 414IPDI PCD1K_0.29 BD_0.56 DMAPD_0.16 N/A Lactic acid 100% N/A 355 IPDIPCD1K_0.29 BD_0.27 DMBA_0.22 DMAPD_0.22 Na₂CO₃ 100% N/A 362 IPDIPCD1K_0.29 BD_0.27 DMAPD_0.22 DMBA_0.22 Lactic acid 100% N/A 372 IPDIPCD1K_0.29 BD_0.27 DMAPD_0.22 DMBA_0.22 Lactic acid 100% Linoleic acidPCD1K = polycarbonate diol with molecular weight at 1,000 g/mol; PCD3K =polycarbonate diol with molecular weight at 3,000 g/mol.

Overall, inventive cationic waterborne polyurethanes possessed optimalphysical properties as defined herein: (1) Young's modulus >150 MPa, (2)Elongation at break between 15% and 300%, and (3) Water uptake (a) below10% for WBPUs without additive (b) below 8% for WBPUs with additive. SeeTable 2.

TABLE 2 Young's Elongation at break PU Name Modulus (MPa) (%) WaterUptake (%) 363 218 ± 21 292 ± 21 8.01 ± 0.20 399 268 ± 10 255 ± 43 7.72± 0.26 400 326 ± 2   24 ± 23 7.55 ± 0.40 377 253 ± 10  95 ± 10 5.23 ±0.40 404 173 ± 22 253 ± 41 5.27 ± 0.37 378 228 ± 15 163 ± 22 3.26 ± 0.33383 198 ± 12 172 ± 48 2.46 ± 0.16 398 145 ± 11 242 ± 10 2.86 ± 0.25 402170 ± 7  47 ± 7 1.51 ± 0.17 376 266 ± 12 307 ± 25 7.51 ± 0.21 355 318 ±24  62 ± 21 5.91 ± 0.47 362 295 ± 10 170 ± 41 2.88 ± 0.93 372 319 ± 42150 ± 45 2.87 ± 0.56 413 340 10 6.22 ± 0.08 414 146 ± 12 216 ± 6  3.61 ±0.11

Particle size and distribution of cationic waterborne polyurethanes canbe divided by two types. Depending on chemical compositions, one type ofcationic waterborne polyurethanes showed uniform particle sizedistribution and average particle diameter was in the range of about 20to about 80 nm. The other type of cationic waterborne polyurethaneshowed large particle size and bimodal/multimodal particle sizedistribution as indicated by average particle sizes in the range of 100to approximately 300 nm and large standard deviation of particle size.See Table 3.

TABLE 3 PU Particle Size Name (TEM, nm) 363 29.8 ± 3.9  399 29.9 ± 4.3 400 29.6 ± 5.0  377 34.1 ± 7.5  378 36.6 ± 10.7 383 150.3 ± 112.9 398111.2 ± 45.4  402 139.6 ± 50.6  376 21.3 ± 4.5  355 41.3 ± 18.3 362 57.0± 15.6 372 79.7 ± 29.7 413 60.1 ± 16.7 414 106.2 ± 25.2 

Example 2. Mechanical Performance

The Young's modulus is a measure of the ability of a material towithstand changes in length when under uniaxial tension or compression.A higher Young's modulus typically indicates that the material is morerigid. The elongation at break, also known as fracture strain, is theratio between changed length and initial length after breakage of thetest specimen. A higher elongation at break expresses the capability ofa material to resist fracture. For a composition applied to hair to holdthe shape of the hair, the Young's modulus and elongation at break ofthe composition should be such that the composition provides rigidity tothe hair but is not brittle.

A comparison of Young's modulus and the elongation at break for the someof the polyurethanes disclosed herein was made to several commerciallyavailable polyurethane products. The Young's modulus and the elongationat break can be determined by a protocol defined to measure mechanicalproperties is developed in compliance with ASTM D638, ASTM D412, testguidelines. In particular, the following protocol can be used todetermine the Young's modulus and elongation at break (or ultimateelongation) of dry film of polyurethanes. Testing requires approximately10-20 min per sample to complete.

Materials:

>25 g polyurethane aqueous dispersion

1 clean rectangular mold (2 mm×20 mm×45 mm) grooved on Teflon sheet persample

1 clean razor blade

Scotch tape

Universal Testing Machine mounted with extension grip geometry

Sample Preparation:

-   -   1. Prepare 25 g of 10 wt % WBPU solution from their respective        stock solution.    -   2. Apply 2.5 mL prepared solution in each mold (2 mm×20        mm×45 mm) and allow drying for 2 days to give WBPU film.    -   3. After it dries out, use a spatula to remove film from the        mold.    -   4. Use the razor blade to cut corners and get film with around        15 mm width and around 150-300 micron thickness. Make sure that        the film is free of air bubbles.    -   5. Label the test film.    -   6. Cut four pieces of tape (20 mm) per sample and adhere them to        both sides of the specimen strip and make a dog-bone shaped        sample to improve hold of sample in grip. Store the prepared        test films in desiccators for 1-2 hour to fully dry them. Take        one sample out of desiccators at a time for testing.

Sample Testing

-   -   1. Balance the load registering on the universal testing machine        so that it reads 0 Newtons.    -   2. Use calipers to set a distance of 20 mm between the top and        bottom extension grip geometries.    -   3. Mount a sample in the extension grips and secure tightly,        ensuring that the scotch tape is not visible, and that the        sample is as close to vertical as possible in both vertical        planes.    -   4. Stretch the sample slightly, by separating the geometries        until a force of 2-5 N is registered.    -   5. Begin a tensile testing run on the universal testing machine        at a speed of 100 mm/minute, stopping the test upon sample        fracture.    -   6. Elongation at break is calculated at the elongation at which        the material fractures.    -   7. Young's modulus is calculated as the modulus during the        initial, elastic portion of deformation by calculating the slope        of a linear fit to that region with an R value >0.99.    -   a) low modulus and high elongation (Avalure UR 450, C1004,        Polyderm PE/PA ED, Polyderm PE/PA), which leads to inferior curl        hold (e.g., hold is temporary, transient, or short-lived) or    -   b) high modulus and low elongation (DynamX, DynamX/H₂O, Luviset        PUR), which leads to a brittle material with low performance        (e.g., resin is brittle or fractures) after manipulation.

Example 3. Hydrophobicity/Water Uptake of Polyurethane

The moisture uptake properties, under highly humid environment, of WBPUdry films have been linked to their long lasting hold performance. Assuch, it is important to be able to reproducibly and accurately evaluatesuch moisture uptake properties to enable predictive in vitro and invivo evaluation of WBPU dry films. The following protocol can be used todetermine moisture uptake ability of WBPU dry films under high humidenvironment. Test requires about 2-3 days per sample set to complete

Materials

>15 g WBPU solution

1 clean cell culture petri dish (60 mm dia×15 mm H) per sample

Humidity chamber with flexibility to control temperature and relativehumidity (RH)

Sample Testing

-   -   1. Prepare 15 g of 10 wt % WBPU solution from their respective        stock solution.    -   2. Label cell culture petri dishes for each sample and measure        their empty weight (W_(pd)).    -   3. Apply 4 mL prepared solution in each petri dish (3 samples        per WBPU and allow to equilibrate for 20 hours at 25° C. and 50%        RH in humidity chamber.    -   4. After equilibration, measure and record sample weight (Wi).    -   5. Place the samples to humidity chamber at 25° C. and 90% RH        and allow equilibration to high humidity for 20 hours.    -   6. Measure and record final sample weight (W).

Sample Analysis

Calculate % moisture uptake using the following equation:

${\% \mspace{14mu} {moisture}\mspace{14mu} {uptake}} = {\left\lbrack \frac{\left( {\left( {{Wf} - {Wpd}} \right) - \left( {{Wi} - {Wpd}} \right)} \right)}{\left( {{Wi} - {Wpd}} \right)} \right\rbrack \times 100\%}$

Example 4. Two Wave Styling

Since the isoelectric point (IEP, the pH at which a molecule or asubstance carries no net electrical charge) of hair is about 3.67 (seeChemical and Physical Behavior of Human Hair, 5^(th) ed.; p 388), thesurface of hair bears a net negative charge at pHs above its IEP, wheremost hair care products are formulated. Anionic WBPUs which are oftenused in different hair care products, are therefore more likely to bindto hair surfaces by polar and Van der Waals interactions (see Chemicaland Physical Behavior of Human Hair). By contrast, cationic WBPUs thatcarry opposite charges such as those described herein can bind to hairsurfaces through the formation of ionic bonds. To achieve more enhancedperformance, a new two-wave styling technology was developed, in whichcationic and anionic WBPUs are used together to create synergisticstyling properties. The detailed mechanism is shown in FIG. 1. Hairsurface naturally bears a net negative charge. Therefore cationic WBPUs,when applied as the first layer, are readily attracted to hair surface,providing strong hold to hair and creating the so-called a first wavestyling. To take advantage of the excess positive charges of thecationic WBPU particles, a second layer of anionic WBPU particles isthen deposited. The ionic interaction between the cationic and anionicWBPUs further enhances the hold and provides a second wave of styling.

Tress Testing

To test the two-wave styling concept, systematic in vitro testing ofcationic and anionic WBPUs was conducted. In all in vitro testing, acationic WBPU was applied to a tress as an aqueous dispersion at 3 wt %polymer, and then an anionic WBPU was applied as an aqueous dispersionsat 3 wt % polymer. The tress was blow dried for 90 seconds, then curledusing ¾″ curling rod at 370° F. for 10 seconds and cooled in coiledformation. The tress was then subjected to 75% relative humidity at 25°C. for 15 minutes and then mechanically stressed by extending the tressto its original length, holding for 1 second, and releasing. Resultsshow that both excellent high humidity curl retention and good sensoryproperties could be achieved.

As a preliminary screening, cationic and anionic WBPUs that were appliedeither in the first or second wave were tested alone. Results showedthat cationic WBPU PU 363 showed better curl length and curl shaperetention after high humidity. This was attributed to the strong ionicinteractions between the WBPU, which has a relatively high cationiccharge density, and inherently anionic hair surfaces. Further screeningof all cationic WBPUs of different cationic charge densities showed thatcationic WBPUs with higher charge densities provide better high heatcurl retention (PU 363, PU 377, and PU 378).

When applied in a two-wave process where a cationic WBPU is firstapplied to the hair tress, a curl is styled, followed by the applicationof spray carrying an anionic WBPU; excellent high humidity curlretention was achieved. FIG. 2a shows an example of hair tresses beforeand after high humidity test styled using two-wave cationic/anionic WBPUapplication as described above. Set B, where 0.8 g of the cationic WBPUPU 363 was applied initially at a 3 wt % polymer concentration followedby 0.4 g of anionic WBPU, also at 3 wt % solid polymer concentration,showed the best initial hold and curl retention after high humidity asopposed to the tresses styled using cationic (+) alone or anionic (−)alone WBPUs only or anionic followed by cationic ((−)/(+)) WBPUapplication (FIG. 2b ). This supports two-wave styling concept where atfirst strong ionic interactions are formed between anionic hair surfacesand cationic WBPU dispersions followed by additional ionic interactionsof cationic WBPU dispersions with anionic WBPU dispersions creatinglong-lasting curl style. Mannequin Testing

In addition to the testing on hair tresses, extensive mannequin testingwas conducted to evaluate the hold, sensory properties, and visualeffects of the cationic polyurethanes. Both cationic and anionic WBPUscan be applied as either aqueous dispersions (FIG. 3) or in differentstyling formulations (FIG. 4). The results in FIG. 3 and FIG. 4 showthat two-wave styling (cationic followed by anionic (+/−)) led tosuperior performance (better hold and high humidity curl retention).Performance using only anionic WBPU dispersions in both waves is shownby (−/−). All dispersions were applied at a 3 wt % WBPU concentration.The two-wave styling (+/−) was carried out using a representativecationic PU 377, and anionic WBPU dispersions as the second wave.Anionic dispersions that can be used are found in PCT/US2017/021025. InFIG. 4, the two-wave styling (+/−) was carried out using NoFrizzConditioner (available from Living Proof, Cambridge Mass.) containing acationic WBPU (PU 377) as the first wave and an anionic WBPU dispersionas the second wave, and showed better performance compared to using thecontrol NoFrizz conditioner as the first wave and anionic WBPU as thesecond wave (Ctrl/−).

In Vivo Performance

To validate the in vitro results, and to assess performance under normalhair care product use conditions, cationic and anionic WBPUs wereapplied as either 3 wt % aqueous dispersions or in different stylingformulations. Although performance differences are less pronounced whencompared with highly controlled in vitro testing, two-wave styling didconsistently show improved performance compared to other stylingmethods, e.g., only anionic WBPU in both waves, in achieving strong holdand high humidity curl retention. See FIG. 5. The two-wave styling(cationic followed by anionic (+/−)) was carried out using the cationicWBPU dispersion PU 377, as the first wave and the anionic WBPUdispersion as the second wave, which showed better performance comparedto using only the anionic WBPU dispersions in both waves (−/−). Alldispersions were applied at a 3 wt % WBPU concentration.

When the cationic and the anionic WBPUs were incorporated into NoFrizzConditioner or Curl Defining Styling Cream (available from Living Proof,Cambridge Mass.), respectively, the two-wave styling provided muchbetter natural curl definition compared to the current formulations. SeeFIG. 6. The two-wave styling (+/−) was carried out using NoFrizzConditioner containing a cationic WBPU (PU 377) as the first wave andCurl Defining Styling Cream containing an anionic WBPU as the secondwave, and showed much better curl definition compared to using NoFrizzConditioner as the first wave and Curl Defining Styling Cream as thesecond wave (Ctrl).

Example 5. Showering Conditioner

In order to create a long-lasting hairstyle, a consumer must typicallyexpend additional time and energy applying dedicated styling products totheir hair after shampooing and conditioning. For many consumers,spending the time to apply these additional styling products is notfeasible or desirable. Thus, there is a need in the market for moreuser-friendly, time-saving styling products. The cationic polyurethanesdescribed herein can be leveraged to address this problem.

Hair conditioners are typically low pH (<7) formulations containingsmoothening and conditioning molecules functionalized with positivelycharged quaternium functional groups, and are therefore incompatiblewith traditional anionic styling polymers used widely in the industry.However, when the cationic polyurethanes described herein are formulatedin conditioners or leave-in-conditioners, the formulations were found toprovide excellent style hold in addition to smoothing and conditioning.See e.g., FIG. 7 and FIG. 8.

Table 4 shows an exemplary list of conditioners andleave-in-conditioners comprising the disclosed cationic polyurethanes.

TABLE 4 Cationic WBPU Wt % Incorporated WBPU Type of Formulation 363 5Conditioner 362 5 Conditioner 376 5 Conditioner 377 5 Conditioner 378 5Conditioner 377 10 Conditioner 377 5 Leave-In Conditioner 404 10Conditioner

When conditioners containing the disclosed cationic polyurethanes areused in place of conditioners without the cationic polyurethanes, curlhold was significantly improved. FIG. 7 shows an example of the curlsgenerated using a hot curling iron after washing with either conditionercontaining 5% cationic polyurethane PU 363 (left) or with the sameconditioner base without a cationic polyurethane. Because the cationicpolyurethane styling polymer can be formulated directly into theconditioner, the consumer can achieve long-lasting styles withoutneeding a separate styling product.

In addition to curl hold, conditioners containing the disclosed cationicpolyurethanes can provide hold and stylability for blowout styles inwhich a stylist brushes the hair while blow drying in order to providebounce, body and shape to the hair. FIG. 8, for example, shows thesuperior stylability of hair washed with a conditioner containing acationic polyurethane PU 363 (left) vs. hair washed with a conditionerwithout a cationic WBPU (right).

The incorporation of the disclosed cationic polyurethanes intoconditioner also improves the smooth appearance of hair and minimizesflyaways, presumably by providing a thin, stiff coating around the hairfiber and serving as a hydrophobic layer that helps hairs maintain theirstraight style after blow drying. FIG. 9, for example, shows thatconditioner containing 5% amphoteric/cationic polyurethane PU 362provides significant flyaway minimization (right) compared to controlconditioner (left).

Finally, conditioners containing cationic polyurethanes as describedherein preserve curl shape in naturally curly-haired consumers. FIG. 10,for example, shows the relative curl enhancement that can be attainedwith use of the amphoteric/cationic polyurethane PU 362 conditioner(right), in contrast to the poor curl enhancement observed with use of ablank conditioner (left).

The contents of all references (including literature references, issuedpatents, published patent applications, and co-pending patentapplications) cited throughout this application are hereby expresslyincorporated herein in their entireties by reference. Unless otherwisedefined, all technical and scientific terms used herein are accorded themeaning commonly known to one with ordinary skill in the art.

1. A hair treatment composition comprising a cationic polyurethanehaving a Young's modulus above 150 MPa, an elongation at break fromabout 15% to about 300%, and a moisture uptake of less than 10%. 2.(canceled)
 3. The composition of claim 1, wherein the cationicpolyurethane is a salt of the formula: [W, V, Y and Z]X⁻, wherein W isthe product formed from polycarbonate polyol monomer; V is the productformed from polyisocyanate monomer; Y is the product formed fromC₁₋₈alkyldiol monomer; Z is the product formed from C₁₋₈aminoalkyldiolmonomer; X is a neutralizing ion; the molecular weight of W is about1,000 g/mol; the molar ratio of V:W is 1:0.18 to about 1:0.32; the molarratio of V:Y is 1:0.24 to about 1:0.72; and the molar ratio of V:Z is1:0.08 to about 1:0.47.
 4. The composition of claim 1, wherein thecationic polyurethane is a salt of the formula: [W, V, Y and Z]X⁻,wherein W is the product formed from polycarbonate polyol monomer; V isthe product formed from polyisocyanate monomer; Y is the product formedfrom C₁₋₈alkyldiol monomer; Z is the product formed fromC₁₋₈aminoalkyldiol monomer; X is a neutralizing ion; the molecularweight of W is about 2,000 g/mol; the molar ratio of V:W is 1:0.08 toabout 1:0.18; the molar ratio of V:Y is 1:0.36 to about 1:0.82; and themolar ratio of V:Z is 1:0.08 to about 1:0.49.
 5. The composition ofclaim 1, wherein the cationic polyurethane is a salt of the formula: [W,V, Y and Z]X⁻, wherein W is the product formed from polycarbonate polyolmonomer; V is the product formed from polyisocyanate monomer; Y is theproduct formed from C₁₋₈alkyldiol monomer; Z is the product formed fromC₁₋₈aminoalkyldiol monomer; X is a neutralizing ion; the molecularweight of W is about 3,000 g/mol; the molar ratio of V:W is 1:0.05 toabout 1:0.13; the molar ratio of V:Y is 1:0.4 to about 1:0.85; and themolar ratio of V:Z is 1:0.08 to about 1:0.49.
 6. The composition ofclaim 1, wherein the cationic polyurethane is a salt of the formula: [W,V, Y, Z, and Z¹]X⁻, wherein W is the product formed from polycarbonatepolyol monomer; V is the product formed from polyisocyanate monomer; Yis the product formed from C₁₋₈alkyldiol monomer; Z is the productformed from C₁₋₈aminoalkyldiol monomer; Z¹ is the product formed fromethoxylated polyol monomer; X is a neutralizing ion; the molecularweight of W is about 1,000 g/mol; the molar ratio of V:W is 1:0.19 toabout 1:0.33; the molar ratio of V:Y is 1:0.19 to about 1:0.7; the molarratio of V:Z is 1:0.08 to about 1:0.49; and the molar ratio of V:Z¹ is1:0 to about 1:0.03.
 7. The composition of claim 1, wherein the cationicpolyurethane is a salt of the formula: [W, V, Y, Z, and Z¹]X⁻, wherein Wis the product formed from polycarbonate polyol monomer; V is theproduct formed from polyisocyanate monomer; Y is the product formed fromC₁₋₈alkyldiol monomer; Z is the product formed from C₁₋₈aminoalkyldiolmonomer; Z¹ is the product formed from ethoxylated polyol monomer; X isa neutralizing ion; the molecular weight of W is about 2,000 g/mol themolar ratio of V:W is 1:0.09 to about 1:0.18; the molar ratio of V:Y is1:0.31 to about 1:0.8; the molar ratio of V:Z is 1:0.09 to about 1:0.51;and the molar ratio of V:Z¹ is 1:0 to about 1:0.03.
 8. The compositionof claim 1, wherein the cationic polyurethane is a salt of the formula:[W, V, Y, Z, and Z¹]X⁻, wherein W is the product formed frompolycarbonate polyol monomer; V is the product formed frompolyisocyanate monomer; Y is the product formed from C₁₋₈alkyldiolmonomer; Z is the product formed from C₁₋₈aminoalkyldiol monomer; Z¹ isthe product formed from ethoxylated polyol monomer; X is a neutralizingion; the molecular weight of W is about 3,000 g/mol the molar ratio ofV:W is 1:0.05 to about 1:0.13; the molar ratio of V:Y is 1:0.36 to about1:0.83; the molar ratio of V:Z is 1:0.09 to about 1:0.52; and the molarratio of V:Z¹ is 1:0 to about 1:0.03.
 9. The composition of claim 1,wherein the cationic polyurethane is a salt of the formula: [W, V, Y, Z,and Z²]X⁻, wherein W is the product formed from polycarbonate polyolmonomer; V is the product formed from polyisocyanate monomer; Y is theproduct formed from C₁₋₈alkyldiol monomer; Z is the product formed fromC₁₋₈aminoalkyldiol monomer; Z² is the product formed from hydroxylatedalkyl acid monomer; X is a neutralizing ion; the molecular weight of Wis about 1,000 g/mol; the molar ratio of V:W is 1:0.19 to about 1:0.33;the molar ratio of V:Y is 1:0.14 to about 1:0.44; the molar ratio of V:Zis 1:0.08 to about 1:0.47; and the molar ratio of V:Z² is 1:0.05 toabout 1:0.33.
 10. The composition of claim 1, wherein the cationicpolyurethane is a salt of the formula: [W, V, Y, Z, and Z²]X⁻, wherein Wis the product formed from polycarbonate polyol monomer; V is theproduct formed from polyisocyanate monomer; Y is the product formed fromC₁₋₈alkyldiol monomer; Z is the product formed from C₁₋₈aminoalkyldiolmonomer; Z² is the product formed from hydroxylated alkyl acid monomer;X is a neutralizing ion; the molecular weight of W is about 2,000 g/mol;the molar ratio of V:W is 1:0.09 to about 1:0.18; the molar ratio of V:Yis 1:0.26 to about 1:0.53; the molar ratio of V:Z is 1:0.09 to about1:0.49; and the molar ratio of V:Z² is 1:0.05 to about 1:0.35.
 11. Thecomposition of claim 1, wherein the cationic polyurethane is a salt ofthe formula: [W, V, Y, Z, and Z²]X⁻, wherein W is the product formedfrom polycarbonate polyol monomer; V is the product formed frompolyisocyanate monomer; Y is the product formed from C₁₋₈alkyldiolmonomer; Z is the product formed from C₁₋₈aminoalkyldiol monomer; Z² isthe product formed from hydroxylated alkyl acid monomer; X is aneutralizing ion; the molecular weight of W is about 3,000 g/mol; themolar ratio of V:W is 1:0.05 to about 1:0.13; the molar ratio of V:Y is1:0.3 to about 1:0.56; the molar ratio of V:Z is 1:0.09 to about 1:0.5;and the molar ratio of V:Z² is 1:0.05 to about 1:0.35.
 12. (canceled)13. The composition of claim 1, wherein the cationic polyurethane is asalt of the formula:

wherein n is 6 to 21 and m is 19 to
 31. 14. The composition of claim 1,wherein the cationic polyurethane is selected from PU-363, PU-399,PU-400, PU-377, PU-404, PU-378, PU-383, PU-398, PU-401, PU-402, PU-403,PU-385, PU-376, PU-408, PU-409, PU-396, PU-413, PU-414, PU-362, andPU-372.
 15. The composition of claim 1, wherein the cationicpolyurethane is selected from PU-362, PU-376, PU-377, PU-378, andPU-404.
 16. The composition of claim 1, wherein the cationicpolyurethane is selected from PU-363, PU-377, and PU-378.
 17. (canceled)18. (canceled)
 19. The composition of claim 1, wherein the cationicpolyurethane is dispersed in water. 20-23. (canceled)
 24. Thecomposition of claim 1, wherein the composition further comprises aneutralizer. 25-27. (canceled)
 28. The composition of claim 1, whereinthe composition further comprises an oil.
 29. (canceled)
 30. Thecomposition of claim 2, wherein the oil is linoleic acid or a mixture offatty acids. 31-39. (canceled)
 40. A method for styling hair comprisinga) applying the cationic polyurethane based composition according toclaim 1 to the hair; b) heating the hair to a temperature sufficient toinduce curl; and c) applying an anionic polyurethane having a Young'smodulus above 150 MPa, an elongation at break from about 15% to about300%, and a moisture uptake of less than 10%. 41-46. (canceled)